EP0243761B1 - Phenylenethermassen mit verbesserter Farbstabilität - Google Patents

Phenylenethermassen mit verbesserter Farbstabilität Download PDF

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Publication number
EP0243761B1
EP0243761B1 EP87105334A EP87105334A EP0243761B1 EP 0243761 B1 EP0243761 B1 EP 0243761B1 EP 87105334 A EP87105334 A EP 87105334A EP 87105334 A EP87105334 A EP 87105334A EP 0243761 B1 EP0243761 B1 EP 0243761B1
Authority
EP
European Patent Office
Prior art keywords
parts
weight
phenylene ether
composition
phosphite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87105334A
Other languages
English (en)
French (fr)
Other versions
EP0243761A3 (en
EP0243761A2 (de
Inventor
Renate Ingrid Warren
Ronald H. Place
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GE Specialty Chemicals Inc
Original Assignee
GE Specialty Chemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GE Specialty Chemicals Inc filed Critical GE Specialty Chemicals Inc
Publication of EP0243761A2 publication Critical patent/EP0243761A2/de
Publication of EP0243761A3 publication Critical patent/EP0243761A3/en
Application granted granted Critical
Publication of EP0243761B1 publication Critical patent/EP0243761B1/de
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds

Definitions

  • the present invention relates to phenylene ether compositions having improved color stability, and to blends of phenylene ether copolymer (PEC) resins and high impact polystyrene (HIPS) resins in particular.
  • PEC phenylene ether copolymer
  • HIPS high impact polystyrene
  • Phenylene ether resins have long been known as high temperature thermoplastics. These resins are typically prepared by the oxidative coupling of a monohydric phenol such as 2,6-dimethyl phenol. This reaction may be used to synthesize polyphenylene ether homopolymer resins and phenylene ether copolymer resins, such as copolymers of 2,6-dialkyl phenols and 2,3,6-trialkyl phenols. Although these resins have improved thermal resistance, high temperature oxidative stability and resistance to heat aging, these resins may experience a shift in color upon melt processing and exposure to ultraviolet (UV) radiation which may make the resin unacceptable for the intended application.
  • UV ultraviolet
  • UV light stabilizers may include benzophenones, benzotriazoles, organic nickel compounds, and various hindered amines.
  • performance of UV stabilizers may differ depending upon the resin in which they are used and the presence of other components.
  • stabilizers are known for phenylene ether resins, these stabilizers may prove inadequate for many compositions, such as flame retardant phenylene ether resins. Therefore phenylene ether based resin compositions with improved color stability offer significant practical advantages over many compositions known in the art.
  • the present invention is a thermoplastic composition which comprises a triaryl phosphate, an alkyl aryl phosphite, and a resin component which includes a phenylene ether polymer wherein the triaryl phosphate is present in an amount equal to 10 to 30 parts by weight and the alkyl aryl phosphite is present in an amount equal to 0.3 to 6 parts by weight, based on 100 parts by weight of the resin component, or when the thermoplastic composition comprises more than 1 part by weight octyl diphenyl phosphite as the alkyl aryl phosphite, the triaryl phosphate is present in an amount equal to 5 to 30 parts by weight, the parts by weight again based on 100 parts by weight of the resin component.
  • the triaryl phosphate is triphenyl phosphate and the alkyl aryl phosphite is octyl diphenyl phosphite.
  • the present invention is a thermoplastic composition which comprises a triaryl phosphate, an alkyl aryl phosphite and a resin component which includes a phenylene ether polymer.
  • the phenylene ether resin useful for the present invention generally is a polymer of a 2,6-dialkyl phenol, such as 2,6-dimethyl phenol, and copolymers thereof with a 2,3,6-trialkyl phenol, such as 2,3,6-trimethyl phenol.
  • the proportion of 2,3,6-trialkyl phenol will usually be about 2 to about 50% by weight, based on the total weight of the phenylene ether copolymer.
  • the preferred copolymers are those comprising about 2 to about 20, and more preferably about 2 to about 10 wt% 2,3,6-trialkyl phenol and, correspondingly, from about 98 to about 80, and more preferably about 98 to about 90 wt% 2,6-dialkyl phenol.
  • the synthesis of such resins from the corresponding phenols by an oxidative coupling process is well known in the art, and is exemplified in US-A-4,011,200.
  • the phenylene ether polymer useful in the composition of the present invention may be a phenylene ether homopolymer, phenylene ether copolymers are preferred.
  • the resin component additionally includes a vinyl aromatic resin, such as homopolymers of sytrene, vinyl toluene, chlorostyrene, bromostyrene, and copolymers thereof, as well as impact modified versions of the various styrenic resins which typically include graft copolymers of said monomers on rubbery substrates, block copolymers of polystyrene and elastomeric diene blocks and blends of said homopolymers or copolymers with rubbery impact modifiers.
  • High impact polystyrene resins and blends of high impact polystyrene resins with other styrenic resins are most preferred.
  • Styrenic resins useful in the invention are available commercially, or may be synthesized by means well known in the art.
  • blends of polyphenylene ether homopolymers and copolymer resins with styrenic resins are available commercially as Noryl resins sold by the General Electric Company, and Prevex resins sold by Borg-Warner Chemicals, Inc.
  • Vinyl aromatic resins are preferably present in amounts equal to 20 to 70 parts by weight, based on 100 parts by weight of the resin component, and more preferably 30 to 60 parts by weight.
  • the phenylene ether resins and blends of phenylene ether resins with vinyl aromatic resins may be formulated to include plasticizers, pigments, flame retardants, lubricants, stabilizers and the like, such as polyolefins, phenolic stabilizers, and so forth.
  • thermoplastic composition include both a triaryl phosphate and an alkyl aryl phosphite.
  • triaryl phosphates are known in the art, and include compounds such as triphenyl phosphate, t-butylphenyl diphenyl phosphate, cresyl diphenyl phosphate, isopropylphenyl diphenyl phosphate, tricresyl phosphate and trixylenyl phosphate.
  • triphenyl phosphate is preferred.
  • Amounts of triaryl phosphate of about 10 to about 20 parts by weight are preferred.
  • alkyl aryl phosphites include compounds such as decyl diphenyl phosphite, octyl diphenyl phosphite, didecyl phenyl phosphite, neopentyl nonylphenyl phosphite, and neopentyl phenyl phosphite.
  • octyl diphenyl phosphite is preferred.
  • the alkyl aryl phosphite be present in amounts more than 1 part by weight based on 100 parts by weight of the resin component. Amounts of the alkyl aryl phosphite equal to about 1.5 to about 3 parts by weight are more preferred, with amounts of about 2 to about 2.5 parts by weight being particularly preferred.
  • compositions consistent with various embodiments of the invention wherein the composition includes a triaryl phosphate, an alkyl aryl phosphite and a phenylene ether polymer, were tested to assess their color stability when exposed to UV radiation.
  • Samples were tested by exposure to UV radiation from a carbon arc lamp for 125 fadeometer hours (SFH), or by exposure to UV radiation from a xenon arc lamp for 100 xenon fadeometer hours (XFH), or by HPUV exposure at 38% (HPUV 38%), and the change in color or "Delta E" noted.
  • compositions tested their proportions in parts by weight (pbw) and the results of testing are indicated below in Tables I - VI. All compositions included 0.6 pbw of a hindered phenolic antioxidant and 0.5 pbw of a lubricant.
  • PEC denotes a phenylene ether copolymer of approximately 95% 2,6-dimethyl phenol and approximately 5% 2,3,6-trimethyl phenol.
  • HIPS denotes high impact polystyrene; and
  • TPPA denotes triphenyl phosphate.
  • IM denotes rubbery impact modifier
  • TNPP denotes tris-nonylphenyl phosphite
  • ODPP denotes octyl diphenyl phosphite
  • UV 180 denotes Noryl ⁇ UV 180, a phenylene ether polymer/styrenic polymer blend available from the General Electric Co.
  • Cyasorb UV 531 denotes 2-hydroxy-4-n-octoxybenzophenone obtained from American Cyanamid
  • "Irganox MD1024" denotes a phenolic antioxidant available from Ciba-Geigy
  • Et2NOH denotes N, N-diethyl hydroxylamine
  • Teinuvin P denotes 2-(2'-hydroxy-5'-methylphenyl) benzotriazole
  • Teinuvin 328 denotes 2-(2'-hydroxy-3,5'-di-tamylphenyl) benzotriazole
  • Goodrite 3114 denotes an antioxidant available under that designation from the B. F.
  • compositions represented in Examples 1-14 and 19-25 contained minor amounts of pigment sufficient to cause the test specimens to be of a uniform color.
  • Comparative Examples 1 and 3 include tris-nonylphenyl phosphite, instead of the alkyl aryl phosphite as in the present invention.
  • Examples 2 and 4-6 represent various embodiments of the invention, wherein the thermoplastic composition includes a phenylene ether polymer, a triaryl phosphate and an alkyl aryl phosphite.
  • Comparative Example 5 does not contain the triaryl phosphate required according to the present invention.
  • Examples 2, 4 and 7-14 represented in Table II are consistent with various embodiments of the invention, with the alkyl aryl phosphite being present in various proportions in relation to the other components.
  • Examples 15-16 in Table III are consistent with several different embodiments of the invention. However, unlike the present invention, a triaryl phosphate was not present in the composition tested for Comparative Example 17. Similarly, Comparative Example 18 does not embody the invention, but provides a basis for comparing the present invention with ABS or a commercially available phenylene ether polymer composition.
  • Comparative Examples 19, 21, 22, 24 and 26 represent compositions not embodying the invention, while the compositions of Examples 20, 23 and 25 are consistent with various embodiments of the invention.
  • tris-nonylphenyl phosphite was present instead of an alkyl aryl phosphite.
  • the alkyl aryl phosphite was omitted, without being replaced by another compound.
  • Comparative Example 26 represents a commercially available phenylene ether composition believed not to embody the invention.
  • Examples 45(A-C) - 49(A-C) in Table V represent testing of differently colored compositions consistent with the invention.
  • Each of these compositions was composed of 38.0 parts PEC, 60.8 parts HIPS, 1.2 parts IM, 15.0 parts TPPA, and pigments.
  • ODPP was also included in the parts by weight indicated for each specific example.
  • a standard was provided by testing a composition of the same color which contained the same components, except that 0.4 parts TNPP had been substituted for ODPP.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (8)

  1. Thermoplastische Masse, umfassend ein Triarylphosphat in einer Menge von 10 bis 30 Gewichtsteilen, bezogen auf 100 Gewichtsteile der Harzkomponente, ein Alkylarylphosphit in einer Menge von 0,3 bis 6 Gewichtsteilen, bezogen auf 100 Gewichtsteile der Harzkomponente, und eine Harzkomponente, welche ein Phenylenetherpolymer einschließt, oder das Triarylphosphat in einer Menge von 5 bis 30 Gewichtsteilen, bezogen auf 100 Gewichtsteile der Harzkomponente, wenn die thermoplastische Masse mehr als 1 Gewichtsteil Octyldiphenylphosphit umfaßt.
  2. Masse nach Anspruch 1, in der das Harz ein Phenylenethercopolymer ist.
  3. Masse nach Anspruch 1, in der die Harzkomponente zusätzlich ein vinylaromatisches Harz einschließt.
  4. Masse nach Anspruch 3, in der das vinylaromatische Harz ein kautschukmodifiziertes Polystyrol ist.
  5. Masse nach Anspruch 3, in der das vinylaromatische Harz in einer Menge von 20 bis 70 Gewichtsteilen, bezogen auf 100 Gewichtsteile der Harzkomponente, vorhanden ist.
  6. Masse nach Anspruch 5, in der das vinylaromatische Harz in einer Menge von 30 bis 60 Gewichtsteilen, bezogen auf 100 Gewichtsteile der Harzkomponente, vorhanden ist.
  7. Masse nach Anspruch 1, in der das Alkyldiarylphosphit Octyldiphenylphosphit ist.
  8. Masse nach Anspruch 1 oder 7, in der das Triarylphosphat Triphenylphosphat ist.
EP87105334A 1986-04-21 1987-04-10 Phenylenethermassen mit verbesserter Farbstabilität Expired - Lifetime EP0243761B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US85402486A 1986-04-21 1986-04-21
US854024 1986-04-21

Publications (3)

Publication Number Publication Date
EP0243761A2 EP0243761A2 (de) 1987-11-04
EP0243761A3 EP0243761A3 (en) 1989-01-04
EP0243761B1 true EP0243761B1 (de) 1994-08-17

Family

ID=25317533

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87105334A Expired - Lifetime EP0243761B1 (de) 1986-04-21 1987-04-10 Phenylenethermassen mit verbesserter Farbstabilität

Country Status (5)

Country Link
EP (1) EP0243761B1 (de)
JP (1) JP2607513B2 (de)
KR (1) KR960002970B1 (de)
CA (1) CA1323460C (de)
DE (1) DE3750377T2 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2015525A1 (en) * 1989-08-18 1991-02-18 Gim F. Lee Jr. Thermoplastic compositions which contain polyolefins and polyphenylene ethers, and articles made therefrom
ES2132114T3 (es) * 1991-03-27 1999-08-16 Ciba Sc Holding Ag Procedimiento para estabilizar mezclas de materias plasticas recicladas.
DE19647297A1 (de) 1996-11-15 1998-05-20 Basf Ag Thermooxidationsstabile thermoplastische Formmassen

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4383066A (en) * 1980-04-15 1983-05-10 Mitsubishi Gas Chemical Company, Inc. Polyphenylene ether resin composition
JPS56145945A (en) * 1980-04-15 1981-11-13 Mitsubishi Gas Chem Co Inc Stabilized polyphenylene oxide resin composition
US4405739A (en) * 1981-11-17 1983-09-20 General Electric Company Polyphenylene ether resins and compositions heat stabilized with phosphite compounds
JPS596254A (ja) * 1982-07-05 1984-01-13 Mitsubishi Gas Chem Co Inc ポリフエニレンエ−テル系樹脂組成物
DE3443154A1 (de) * 1984-11-27 1986-05-28 Basf Ag, 6700 Ludwigshafen Selbstverloeschende thermoplastische polyamid-formmassen

Also Published As

Publication number Publication date
JP2607513B2 (ja) 1997-05-07
CA1323460C (en) 1993-10-19
KR870010117A (ko) 1987-11-30
JPS62256861A (ja) 1987-11-09
KR960002970B1 (ko) 1996-03-02
DE3750377T2 (de) 1994-12-01
EP0243761A3 (en) 1989-01-04
DE3750377D1 (de) 1994-09-22
EP0243761A2 (de) 1987-11-04

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